1-alkoxy-polyalkyl-piperidine derivatives and their use as polymerization regulators

ABSTRACT

The present invention relates to 1-alkoxy-polyalkyl-piperidine derivatives containing a structural element of formula (I)  
                 
 
     wherein  
     G 1 , G 2 , G 3 , G 4  are independently C 1 -C 6 alkyl with the proviso that at least one is not methyl or G 1  and G 2  or G 3  and G 4 , or G 1  and G 2  and G 3  and G 4  together form a C 5 -C 12 cycloalkyl group;  
     G 5 , G 6  independently are H, C 1 -C 18 alkyl, phenyl, naphthyl or a group COOC 1 -C 18 alkyl and X represents a group such that the free radical X. derived from X is capable of initiating polymerization of ethylenically unsaturated monomers, with the proviso that compounds A1 and A2 are excluded  
                 
 
     Further subjects of the invention are a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) a 1-alkoxy-polyalkyl-piperidine derivative, a process for polymerizing ethylenically unsaturated monomers, and the use of 1-alkoxy-polyalkyl-piperidine derivatives for controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator X., as well as a process for polymerization are also subjects of the present invention.

[0001] The present invention relates to 1-alkoxy-polyalkyl-piperidinederivatives, a polymerizable composition comprising a) at least oneethylenically unsaturated monomer and b) a 1-alkoxy-polyalkyl-piperidinederivative. Further aspects of the present invention are a process forpolymerizing ethylenically unsaturated monomers, and the use of1-alkoxy-polyalkyl-piperidine derivatives for controlled polymerization.The intermediate N-oxyl derivatives, a composition of the N-oxylderivatives with ethylenically unsaturated monomers and a free radicalinitiator X., as well as a process for polymerization are also subjectsof the present invention.

[0002] The compounds of the present invention provide polymeric resinproducts having low polydispersity. The polymerization process proceedswith enhanced monomer to polymer conversion efficiency. In particular,this invention relates to stable free radical-mediated polymerizationprocesses which provide homopolymers, random copolymers, blockcopolymers, multiblock copolymers, graft copolymers and the like, atenhanced rates of polymerization and enhanced monomer to polymerconversions.

[0003] Polymers or copolymers prepared by free radical polymerizationprocesses inherently have broad molecular weight distributions orpolydispersities which are generally higher than about four. One reasonfor this is that most of the free radical initiators have half livesthat are relatively long, ranging from several minutes to many hours,and thus the polymeric chains are not all initiated at the same time andthe initiators provide growing chains of various lengths at any timeduring the polymerization process. Another reason is that thepropagating chains in a free radical process can react with each otherin processes known as combination and disproportionation, both of whichare irreversibly chain-terminating reaction processes. In doing so,chains of varying lengths are terminated at different times during thereaction process, resulting in resins consisting of polymeric chainswhich vary widely in length from very small to very large and which thushave broad polydispersities. If a free radical polymerization process isto be used for producing narrow molecular weight distributions, then allpolymer chains must be initiated at about the same time and terminationof the growing polymer-chains by combination or disproportionationprocesses must be avoided.

[0004] Conventional radical polymerization reaction processes posevarious significant problems, such as difficulties in predicting orcontrolling the molecular weight, the polydispersity and the modality ofthe polymers produced. These prior art polymerization processes producepolymers having broad polydispersities and in some instances, lowpolymerization rates. Furthermore, free radical polymerization processesin bulk of the prior art are difficult to control because thepolymerization reaction is strongly exothermic and an efficient heatremoval in the highly viscous polymer is mostly impossible. Theexothermic nature of the prior art free radical polymerization processesoften severely restricts the concentration of reactants or the reactorsize upon scale-up.

[0005] Due to the above mentioned uncontrollable polymerizationreactions, gel formation in conventional free radical polymerizationprocesses are also possible and cause broad molecular weightdistributions and/or difficulties during filtering, drying andmanipulating the product resin.

[0006] U.S. Pat. No. 4,581,429 to Solomon et al., issued Apr. 8, 1986,discloses a free radical polymerization process which controls thegrowth of polymer chains to produce short chain or oligomerichomopolymers and copolymers, including block and graft copolymers. Theprocess employs an initiator having the formula (in part) R′R″N—O—X,where X is a free radical species capable of polymerizing unsaturatedmonomers. The reactions typically have low conversion rates.Specifically mentioned radical R′R″N—O. groups are derived from 1,1,3,3tetraethylisoindoline, 1,1,3,3 tetrapropylisoindoline, 2,2,6,6tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine ordi-t-butylamine. However, the suggested compounds do not fulfill allrequirements. Particularly the polymerization of acrylates does notproceed fast enough and/or the monomer to polymer conversion is not ashigh as desired.

[0007] Recently other attempts to develop new polymerization regulatorshave been published. WO 98/4408 and WO 98/30601 disclose heterocycliccompounds suitable for controlled polymerization processes. WO 98/13392discloses open chain alkoxyamines which are derived from NO gas or fromnitroso componds.

[0008] EP-A-735 052 discloses a method for preparing thermoplasticpolymers of narrow poly-dispersities by free radical-initatedpolymerization, which comprises adding a free radical initiator and astable free radical agent to the monomer compound.

[0009] This method has the disadvantage that uncontrollablerecombinations of initiator radicals may occur immediately after theirformation, thus producing variable ratios between initiator radicals andstable free radicals. Consequently in some cases there is no goodcontrol of the polymerization process.

[0010] There is therefore still a need for polymerization processes forthe preparation of narrow polydispersity polymeric resins with definedmolecular weights using the economical free radical polymerizationtechniques. These polymerization processes will also control thephysical properties of the polymers such as viscosity, hardness, gelcontent, processability, clarity, high gloss, durability, and the like.The polymerization processes and resin products of the present inventionare useful in many applications, including a variety of specialtyapplications, such as for the preparation of block copolymers which areuseful as compatibilizing agents for polymer blends, or dispersingagents for coating systems or for the preparation of narrow molecularweight resins or oligomers for use in coating technologies andthermoplastic films or as toner resins and liquid immersion developmentink resins or ink additives used for electrophotographic imagingprocesses.

[0011] Surprisingly, it has now been found that it is possible toovercome the afore mentioned shortcomings of the prior art by providinga polymerizable composition containing specific initiator compounds.Polymerization of the composition results in a polymer or copolymer ofnarrow polydispersity and a high monomer to polymer conversion even atrelatively low temperatures and at short reaction times, making thepolymerization process particularly suitable for industrialapplications. The resulting copolymers are of high purity and in manycases colorless, therefore not requiring any further purification.

[0012] One object of the present invention is to provide a1-alkoxy-polyalkyl-piperidine derivative containing a structural elementof formula (I)

[0013] wherein

[0014] G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl with the proviso thatat least one is not methyl or G₁ and G₂ or G₃ and G₄, or G₁ and G₂ andG₃ and G₄ together form a C₅-C₁₂cycloalkyl group;

[0015] G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or agroup COOC₁-C₁₈alkyl and X represents a group having at least one carbonatom and is such that the free radical X. derived from X is capable ofinitiating polymerization of ethylenically unsaturated monomers, withthe proviso that compounds A1 and A2 are excluded

[0016] The alkyl radicals in the various substituents may be linear orbranched. Examples of alkyl containing 1 to 18 carbon atoms are methyl,ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl,2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

[0017] C₅-C₁₂cycloalkyl is typically, cyclopentyl, methylcyclopentyl,dimethylcyclopentyl, cyclohexyl, methylcyclohexyl.

[0018] Preferred compounds or mixture of compounds are any of formulae Ato S.

[0019] wherein

[0020] G₁, G₂, G₃ and G₄ are independently alkyl of 1 to 4 carbon atoms,or G₁ and G₂ together and G₃ and G₄ together, or G₁ and G₂ together orG₃ and G₄ together are pentamethylene;

[0021] G₅ and G₆ are independently hydrogen or C₁-C₄ alkyl;

[0022] R, if m is 1, is hydrogen, C₁-C₁₈alkyl which is uninterrupted orC₂-C₁₈alkyl which is interrupted by one or more oxygen atoms,cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphaticcarboxylic acid having 2 to 18 carbon atoms, of a cycloaliphaticcarboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturatedcarboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylicacid having 7 to 15 carbon atoms, where each carboxylic acid can besubstituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to3 —COOZ₁₂ groups, in which Z₁₂ is H, C₁-C₂₀alkyl, C₃-C₁₂alkenyl,C₅-C₇cycloalkyl, phenyl or benzyl; or

[0023] R is a monovalent radical of a carbamic acid orphosphorus-containing acid or a monovalent silyl radical;

[0024] R, if m is 2, is C₂-C₁₂alkenylene, C₄-C₁₂alkenylene, xylylene, adivalent radical of an aliphatic dicarboxylic acid having 2 to 36 carbonatoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamicacid having 8-14 carbon atoms, where each dicarboxylic acid may besubstituted in the aliphatic, cycloaliphatic or aromatic moiety by oneor two —COOZ₁₂ groups; or

[0025] R is a divalent radical of a phosphorus-containing acid or adivalent silyl radical;

[0026] R, if m is 3, is a trivalent radical of an aliphatic,cycloaliphatic or aromatic tricarboxylic acid, which may be substitutedin the aliphatic, cycloaliphatic or aromatic moiety by —COOZ₁₂, of anaromatic tricarbamic acid or of a phosphorus-containing acid, or is atrivalent silyl radical,

[0027] R, if m is 4, is a tetravalent radical of an aliphatic,cycloaliphatic or aromatic tetracarboxylic acid;

[0028] p is 1, 2 or 3,

[0029] R₁ is C₁-C₁₂alkyl, C₅-C₇cycloalkyl, C₇-C₈aralkyl, C₂-C₁₈alkanoyl,C₃-C₅alkenoyl or benzoyl;

[0030] when p is 1,

[0031] R₂ is C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₂-C₈alkenyl unsubstituted orsubstituted by a cyano, carbonyl or carbamide group, or is glycidyl, agroup of the formula —CH₂CH(OH)—Z or of the formula —CO—Z— or —CONH—Zwherein Z is hydrogen, methyl or phenyl; or when p is 2,

[0032] R₂ is C₂-C₁₂alkylene, C₆-C₁₂arylene, xylylene, a—CH₂CH(OH)CH₂—O—B—O—CH₂CH(OH)CH₂— group, wherein B is C₂-C₁₀alkylene,C₆-C₁₅arylene or C₆-C₁₂cycloalkylene; or, provided that R₁ is notalkanoyl, alkenoyl or benzoyl, R₂ can also be a divalent acyl radical ofan aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamicacid, or can be the group —CO—; or

[0033] R₁ and R₂ together when p is 1 can be the cyclic acyl radical ofan aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid; or

[0034] R₂ is a group

[0035] where T₇ and T₈ are independently hydrogen, alkyl of 1 to 18carbon atoms, or T₇ and T₈ together are alkylene of 4 to 6 carbon atomsor 3-oxapentamethylene; when p is 3,

[0036] R₂ is 2,4,6-triazinyl;

[0037] when n is 1,

[0038] R₃ is C₂-C₈-alkylene or hydroxyalkylene or C₄-C₂₂acyloxyalkylene;or

[0039] when n is 2,

[0040] R₃ is (—CH₂)₂C(CH₂—)₂;

[0041] when n is 1,

[0042] R₄ is hydrogen, C₁-C₁₂alkyl, C₃-C₅alkenyl, C₇-C₉aralkyl,C₅-C₇cycloalkyl, C₂-C₄hydroxyalkyl, C₂-C₆alkoxyalkyl, C₆-C₁₀aryl,glycidyl, a group of formula —(CH₂)_(m)—COO—Q or of the formula—(CH₂)_(m)—O—CO—Q wherein m is 1 or 2 and Q is C₁-C₄alkyl or phenyl; or

[0043] when n is 2,

[0044] R₄ is C₂-C₁₂alkylene, C₆-C₁₂arylene, a group—CH₂CH(OH)CH₂—O—D—O—CH₂CH(OH)CH₂— wherein D is C₂-C₁₀alkylene,C₆-C₁₅arylene or C₆-C₁₂cycloalkylene, or a group—CH₂CH(OZ₁)CH₂—(OCH₂CH(OZ₁)CH₂)₂— wherein Z₁ is hydrogen, C₁-C₁₈alkyl,allyl, benzyl, C₂-C₁₂alkanoyl or benzoyl;

[0045] R₅ is hydrogen, C₁-C₁₂alkyl, allyl, benzyl, glycidyl orC₂-C₆alkoxyalkyl;

[0046] Q₁ is —N(R₇)— or —O—;

[0047] E is C₁-C₃alkylene, the group —CH₂CH(R₈)—O— wherein R₈ ishydrogen, methyl or phenyl, the group —(CH₂)₃—NH— or a direct bond;

[0048] R₇ is C₁-C₁₈alkyl, C₅-C₇-cycloalkyl, C₇-C₁₂aralkyl, cyanoethyl,C₆-C₁₀-aryl, the group —CH₂CH(R₈)—OH; or a group of the formula

[0049] or a group of the formula

[0050] wherein G is C₂-C₆alkylene or C₆-C₁₂arylene and R is as definedabove; or

[0051] R₇ is a group —E—CO—NH—CH₂—OR₆;

[0052] R₆ is hydrogen or C₁-C₁₈alkyl;

[0053] Formula (F) denotes a recurring structural unit of a oligomerwhere T is ethylene or 1,2-propylene, or is a repeating structural unitderived from an α-olefin copolymer with an alkyl acrylate ormethacrylate;

[0054] k is 2 to 100;

[0055] R₁₀ is hydrogen, C₁-C₁₂alkyl or C₁-C₁₂alkoxy;

[0056] T₂ has the same meaning as R₄;

[0057] T₃ and T₄ are independently alkylene of 2 to 12 carbon atoms, orT₄ is a group

[0058] T₅ is C₂-C₂₂alkylene, C₅-C₇cycloalkylene,C₁-C₄alkylenedi(C₅-C₇cycloalkylene), phenylene orphenylenedi(C₁-C₄alkylene);

[0059] where a, b and c are independently 2 or 3, and d is 0 or 1;

[0060] e is 3 or 4;

[0061] T₇ and T₈ are independently hydrogen C₁-C₁₈alkyl, or T₇ and T₈together are C₄-C₆alkylene or 3-oxapenthamethylene;

[0062] E₁ and E₂, being different, each are —CO— or —N(E₅)—, where E₅ ishydrogen, C₁-C₁₂alkyl or C₄-C₂₂alkoxycarbonylalkyl;

[0063] E₃ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl,said phenyl or said naphthyl substituted by chlorine or by alkyl of 1 to4 carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or saidphenylalkyl substituted by alkyl of 1 to 4 carbon atoms;

[0064] E₄ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthylor phenylalkyl of 7 to 12 carbon atoms; or

[0065] E₃ and E₄ together are polymethylene of 4 to 17 carbon atoms, orsaid polymethylene substituted by up to four alkyl groups of 1 to 4carbon atoms; and

[0066] E₆ is an aliphatic or aromatic tetravalent radical.

[0067] C₃-C₁₂alkenyl is for example propenyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, dodecenyl including their isomers.

[0068] C₇-C₉aralkyl is for example benzyl, phenylpropyl,α,α-dimethylbenzyl or α-methylbenzyl.

[0069] C₂-C₁₈alkyl interrupted by at least one O atom is for example—CH₂—CH₂—O—CH₂—CH₃, —CH₂—CH₂—O—CH₃ or —CH₂—CH₂—O—CH₂—CH₂—CH₂—O—CH₂—CH₃.It is preferably derived from polyethlene glycol. A general descriptionis —((CH₂)_(a)—O)_(b)—H/CH₃, wherein a is a number from 1 to 6 and b isa number from 2 to 10.

[0070] If R is a monovalent radical of a carboxylic acid, it is, forexample, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoylor β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

[0071] If R is a monovalent silyl radical, it is, for example, a radicalof the formula —(C_(j)H_(2j))—Si(Z′)₂Z″, in which j is an integer in therange from 2 to 5, and Z′ and Z″, independently of one another, areC₁-C₄alkyl or C₁-C₄alkoxy.

[0072] If R is a divalent radical of a dicarboxylic acid, it is, forexample, a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl,maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl,butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl orbicycloheptenedicarbonyl radical or a group of the formula

[0073] If R is a trivalent radical of a tricarboxylic acid, it is, forexample, a trimellitoyl, citryl or nitrilotriacetyl radical.

[0074] If R is a tetravalent radical of a tetracarboxylic acid, it is,for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylicacid or of pyromellitic acid.

[0075] If R is a divalent radical of a dicarbamic acid, it is, forexample, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.

[0076] C₁-C₁₈alkanoyl is for example, formyl, propionyl, butyryl,octanoyl, dodecanoyl but preferably acetyl and C₃-C₅alkenoyl is inparticular acryloyl.

[0077] Any C₂-C₁₂alkylene radicals are, for example, ethylene,propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene,octamethylene, decamethylene or dodecamethylene.

[0078] Any C₆-C₁₅arylene substituents are, for example, o-, m- orp-phenylene, 1,4-naphthylene or 4,4′-diphenylene.

[0079] C₆-C₁₂cycloalkylene is, in particular, cyclohexylene.

[0080] Hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substitutedC₁-C₄alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl,2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl,2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.

[0081] Any C₂-C₆alkoxyalkyl substituents are, for example,methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl,ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl,isopropoxyethyl or propoxypropyl.

[0082] Preferably G₆ is hydrogen and G₅ is hydrogen or C₁-C₄alkyl.

[0083] Preferably G₁, G₂, G₃ and G₄ are independently C₁-C₄alkyl, withthe proviso that at least one is different from methyl.

[0084] More preferred G₁ and G₃ are methyl and G₂ and G₄ are ethyl orpropyl.

[0085] In another preferred group of compounds G₁ and G₂ are methyl andG₃ and G₄ are ethyl or propyl.

[0086] Preferably X is selected from the group consisting of —CH₂-aryl,

[0087] (C₅-C₆cycloalkyl)₂CCN, (C₁-C₁₂alkyl)₂CCN, —CH₂CH═CH₂,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₆-C₁₀)aryl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkoxy, (C₁-C₁₂)alkyl-CR₂₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₂₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

[0088] wherein

[0089] R₂₀ is hydrogen or C₁-C₁₂alkyl;

[0090] the aryl groups are phenyl or naphthyl which are unsubstituted orsubstituted with C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy,C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COOC₁-C₁₂alkyl.

[0091] More preferred are compounds, wherein X is selected from thegroup consisting of —CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl,(C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN, —CH₂CH═CH₂,CH₃CH—CH═CH₂(C₁-C₈alkyl)CR₂₀—C(O)-phenyl,(C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈)alkoxy,(C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈)alkyl,(C₁-C₈)alkyl-CR₂₀—C(O)—N-di(C₁-C₈)alkyl, (C₁-C₈)alkyl-CR₂₀—C(O)—NH(C₁-C₈)alkyl, (C₁-C₈)alkyl-CR₂₀—C(O)—NH₂, wherein R₂₀is hydrogen or (C₁-C₈)alkyl.

[0092] Particularly preferred are compounds, wherein X is selected fromthe group consisting of —CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl,(C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂(C₁-C₄alkyl)CR₂₀—C(O)-phenyl, (C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄) alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl.

[0093] In a preferred group of compounds X contains no open chainalkylether group.

[0094] Preferred compounds are those of formula A, B, O or P,particularly preferred of formula A, B or O and more preferred offormula A or B, wherein the substituents have the meanings as definedbefore.

[0095] A preferred group of compounds are those of formula A, B or O,wherein

[0096] m is 1,

[0097] R is hydrogen, C₁-C₁₈alkyl which is uninterrupted or interruptedby one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalentradical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, ofa cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or anα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms;

[0098] p is 1;

[0099] R₁ is C₁-C₁₂alkyl, C₅-C₇cycloalkyl, C7-C₈aralkyl, C₂-C₁₈alkanoyl,C₃-C₅alkenoyl or benzoyl;

[0100] R₂ is C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₂-C₈alkenyl unsubstituted orsubstituted by a cyano, carbonyl or carbamide group, or is glycidyl, agroup of the formula —CH₂CH(OH)—Z or of the formula —CO—Z or —CONH—Zwherein Z is hydrogen, methyl or phenyl.

[0101] Amongst the group of compounds of formula A, B or O those aremore preferred, wherein

[0102] R is hydrogen, C₁-C₁₈alkyl, cyanoethyl, benzoyl, glycidyl, amonovalent radical of an aliphatic, carboxylic acid;

[0103] R₁ is C₁-C₁₂alkyl, C₇-C₈aralkyl, C₂-C₁₈alkanoyl, C₃-C₅alkenoyl orbenzoyl;

[0104] R₂ is C₁-C₁₈alkyl, glycidyl, a group of the formula —CH₂CH(OH)—Zor of the formula —CO—Z, wherein Z is hydrogen, methyl or phenyl.

[0105] A further preference for this subgroup is that G₆ is hydrogen andG₅ is hydrogen or C₁-C₄alkyl, G₁ and G₃ are methyl and G₂ and G₄ areethyl or propyl or G₁ and G₂ are methyl and G₃ and G₄ are ethyl orpropyl.

[0106] In addition for the compounds of formula A, B or O a preferredgroup X is selected from the group consisting of —CH₂-phenyl,CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN,—CH₂CH═CH₂, CH₃CH—CH═CH₂, (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl.

[0107] Most preferred are the compounds of formula (A), wherein G₅ andG₆ are hydrogen or methyl, G₁ and G₃ are methyl and G₂ and G₄ are ethylor G₁ and G₂ are methyl and G₃ and G₄ are ethyl;

[0108] m is 1; R is hydrogen, C₁-C₁₈alkyl or a group—C(O)—(C₂-C₁₈)alkyl; and

[0109] X is —CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl,(C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂(C₁-C₄alkyl)CR₂₀—C(O)-phenyl, (C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄) alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl.

[0110] If R is C₁-C₁₈alkyl, propyl is particularly preferred.

[0111] If R is —C(O)—(C₂-C₁₈)alkyl, —C(O)—C₁₁H₂₃ and —C(O)—C₁₇H₃₅ areparticularly preferred.

[0112] A further subject of the invention is a polymerizablecomposition, comprising

[0113] a) at least one ethylenically unsaturated monomer or oligomer,and

[0114] b) a 1-alkoxy-polyalkyl-piperidine derivative containing astructural element of formula (I)

[0115] wherein

[0116] G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl with the proviso thatat least one is not methyl or G₁ and G₂ or G₃ and G₄, or G₁ and G₂ andG₃ and G₄ together form a C₅-C₁₂cycloalkyl group;

[0117] G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or agroup COOC₁-C₁₈alkyl and X represents a group having at least one carbonatom and is such that the free radical X. derived from X is capable ofinitiating polymerization of ethylenically unsaturated monomers, withthe proviso that compounds A1 and A2 are excluded

[0118] Definitions for the substituents and preferred formulas havealready been given. They apply also for the composition including thepreferences.

[0119] Typically the ethylenically unsaturated monomer or oligomer isselected from the group consisting of ethylene, propylene, n-butylene,i-butylene, styrene, substituted styrene, conjugated dienes, acrolein,vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylicesters, (meth)acrylo-nitriles, (alkyl)acrylamides, vinyl halides orvinylidene halides.

[0120] Preferred ethylenically unsaturated monomers are ethylene,propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene,α-C₅-C₁₈alkene, styrene, α-methyl styrene, p-methyl styrene or acompound of formula CH₂═C(R_(a))—(C═Z)—R_(b), wherein R_(a) is hydrogenor C₁-C₄alkyl, R_(b) is NH₂, O³¹ (Me⁺), glycidyl, unsubstitutedC₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom,or hydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H (CH₃)₂ An⁻;

[0121] An⁻ is a anion of a monovalent organic or inorganic acid;

[0122] Me is a monovalent metal atom or the ammonium ion.

[0123] Z is oxygen or sulfur.

[0124] Examples for R_(a) as C₂-C₁₀₀alkoxy interrupted by at least one Oatom are of formula

[0125] wherein R_(c) is C₁-C₂₅alkyl, phenyl or phenyl substituted byC₁-C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1 to 50.These monomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

[0126] Further examples of suitable acrylate or methacrylate monomersare given below.

[0127] An⁻, wherein An⁻ and R_(a) have the meaning as defined above andR_(e) is methyl or benzyl. An⁻ is preferably Cl⁻, Br⁻ or ⁻O₃S—CH₃.

[0128] Further acrylate monomers are

[0129] Examples for suitable monomers other than acrylates are

[0130] Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and Z isoxygen. Particularly preferred ethylenically unsaturated monomers arestyrene, methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate,tert. butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide ordimethylaminopropyl-methacrylamide.

[0131] Preferably the initiator compound is present in an amount of from0.01 mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-%to 20 mol-% and most preferred in an amount of from 0.5 mol-% to 10mol-% based on the monomer or monomer mixture.

[0132] When monomer mixtures are used mol % is calculated on the averagemolecular weight of the mixture.

[0133] Another subject of the present invention is a process forpreparing an oligomer, a cooligomer, a polymer or a copolymer (block orrandom) by free radical polymerization of at least one ethylenicallyunsaturated monomer or oligomer, which comprises (co)polymerizing themonomer or monomers/oligomers in the presence of an initiator compoundcontaining a structural element of formula (I) under reaction conditionscapable of effecting scission of the O—C bond to form two free radicals,the radical .X being capable of initiating polymerization.

[0134] Preferably scission of the O—C bond is effected by ultrasonictreatment, heating or exposure to electromagnetic radiation, rangingfrom γ to microwaves.

[0135] More preferably the scission of the O—C bond is effected byheating and takes place at a temperature of between 50° C. and 160° C.

[0136] The process may be carried out in the presence of an organicsolvent or in the presence of water or in mixtures of organic solventsand water. Additional cosolvents or surfactants, such as glycols orammonium salts of fatty acids, may be present. Other suitable cosolventsare described hereinafter.

[0137] Preferred processes use as little solvents as possible. In thereaction mixture it is preferred to use more than 30% by weight ofmonomer and initiator, particularly preferably more than 50% and mostpreferrably more than 80%.

[0138] If organic solvents are used, suitable solvents or mixtures ofsolvents are typically pure alkanes (hexane, heptane, octane,isooctane), hydrocarbons (benzene, toluene, xylene), halogenatedhydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethyleneglycol, ethylene glycol monomethyl ether), esters (ethyl acetate,propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutylether, ethylene glycol dimethyl ether), or mixtures thereof.

[0139] The aqueous polymerization reactions can be supplemented with awater-miscible or hydrophilic cosolvent to help ensure that the reactionmixture remains a homogeneous single phase throughout the monomerconversion. Any water-soluble or water-miscible cosolvent may be used,as long as the aqueous solvent medium is effective in providing asolvent system which prevents precipitation or phase separation of thereactants or polymer products until after all polymerization reactionshave been completed. Exemplary cosolvents useful in the presentinvention may be selected from the group consisting of aliphaticalcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,polypropylene glycols, amides, carboxylic acids and salts thereof,esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,hydroxyether derivatives such as butyl carbitol or cellosolve, aminoalcohols, ketones, and the like, as well as derivatives thereof andmixtures thereof. Specific examples include methanol, ethanol, propanol,dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol,dipropylene glycol, tetrahydrofuran, and other water-soluble orwater-miscible materials, and mixtures thereof. When mixtures of waterand water-soluble or water-miscible organic liquids are selected as theaqueous reaction media, the water to cosolvent weight ratio is typicallyin the range of about 100:0 to about 10:90.

[0140] The process is particularly useful for the preparation of blockcopolymers. Block copolymers are, for example, block copolymers ofpolystyrene and polyacrylate (e.g., poly(styrene-co-acrylate) orpoly(styrene-co-acrylate-co-styrene). They are usefull as adhesives oras compatibilizers for polymer blends or as polymer toughening agents.Poly(methylmethacrylate-co-acrylate) diblock copolymers orpoly(methylacrylate-co-acrylate-co-methacrylate) triblock copolymers)are useful as dispersing agents for coating systeme, as coatingadditives (e.g. rheological agents, compatibilizers, reactive diluents)or as resin component in coatings(e.g. high solid paints) Blockcopolymers of styrene, (meth)acrylates and/or acrylonitrile are usefulfor plastics, elastomers and adhesives.

[0141] Furthermore, block copolymers of this invention, wherein theblocks alternate between polar monomers and non-polar monomers, areuseful in many applications as amphiphilic surfactants or dispersantsfor preparing highly uniform polymer blends. The (co)polymers of thepresent invention may have a number average molecular weight from 1 000to 400 000 g/mol, preferably from 2 000 to 250 000 g/mol and, morepreferably, from 2 000 to 200 000 g/mol. When produced in bulk, thenumber average molecular weight may be up to 500 000 (with the sameminimum weights as mentioned above). The number average molecular weightmay be determined by size exclusion chromatography (SEC), gel permeationchromatography (GPC), matrix assisted laser desorption/ionization massspectrometry (MALDI-MS) or, if the initiator carries a group which canbe easily distinguished from the monomer(s), by NMR spectroscopy orother conventional methods.

[0142] The polymers or copolymers of the present invention havepreferably a polydispersity of from 1.0 to 2, more preferably of from1.1 to 1.9 and most preferably from 1.2 to 1.8.

[0143] Thus, the present invention also encompasses in the synthesisnovel block, multi-block, star, gradient, random, hyperbranched anddendritic copolymers, as well as graft or copolymers.

[0144] The polymers prepared by the present invention are useful forfollowing applications:

[0145] adhesives, detergents, dispersants, emulsifiers, surfactants,defoamers, adhesion promoters, corrosion inhibitors, viscosityimprovers, lubricants, rheology modifiers, thickeners, crosslinkers,paper treatment, water treatment, electronic materials, paints,coatings, photography, ink materials, imaging materials,superabsorbants, cosmetics, hair products, preservatives, biocidematerials or modifiers for asphalt, leather, textiles, ceramics andwood.

[0146] Because the present polymerizaton is a “living” polymerization,it can be started and stopped practically at will. Furthermore, thepolymer product retains the functional alkoxyamine group allowing acontinuation of the polymerization in a living matter. Thus, in oneembodiment of this invention, once the first monomer is consumed in theinitial polymerizing step a second monomer can then be added to form asecond block on the growing polymer chain in a second polymerizationstep. Therefore it is possible to carry out additional polymerizationswith the same or different monomer(s) to prepare multi-block copolymers.Furthermore, since this is a radical polymerization, blocks can beprepared in essentially any order. One is not necessarily restricted topreparing block copolymers where the sequential polymerizing steps mustflow from the least stabilized polymer intermediate to the moststabilized polymer intermediate, such as is the case in ionicpolymerization. Thus it is possible to prepare a multi-block copolymerin which a polyacrylonitrile or a poly(meth)-acrylate block is preparedfirst, then a styrene or butadiene block is attached thereto, and so on.

[0147] Furthermore, there is no linking group required for joining thedifferent blocks of the present block copolymer. One can simply addsuccessive monomers to form successive blocks.

[0148] A plurality of specifically designed polymers and copolymers areaccessible by the present invention, such as star and graft (co)polymersas described, inter alia, by C. J. Hawker in Angew. Chemie, 1995, 107,pages 1623-1627, dendrimers as described by K. Matyaszewski et al. inMacrmolecules 1996, Vol 29, No. 12, pages 4167-4171, graft (co)polymersas described by C. J. Hawker et al. in Macromol. Chem. Phys. 198,155-166(1997), random copolymers as described by C. J. Hawker inMacromolecules 1996, 29, 2686-2688, or diblock and triblock copolymersas described by N. A. Listigovers in Macromolecules 1996, 29, 8992-8993.

[0149] A further subject of the present invention is a polymer oroligomer, having attached at least one initiator group —X and at leastone oxyamine group of formula (Ia)

[0150] (Ia), wherein G₁, G₂, G₃, G₄, G₅ and G₆ are as defined above,obtainable by the above described process.

[0151] The compounds of formula (I) may be prepared from thecorresponding nitroxides, which are therefore intermediates for thecompounds of formula (I).

[0152] Therefore still another subject of the present invention is a1-oxy-polyalkyl-piperidine derivative containing a structural element offormula (II)

[0153] wherein

[0154] G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl with the proviso thatat least one is not methyl or G₁ and G₂ or G₃ and G₄, or G₁ and G₂ andG₃ and G₄ together form a C₅-C₁₂ cycloalkyl group;

[0155] G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or agroup COOC₁-C₁₈alkyl, with the proviso that compounds B1, B2 and B3 areexcluded

[0156] Definitions for the substituents as well as their preferenceshave already been given. They apply also for the compounds of formula(II). In particular the corresponding formulas (A) to (S) and theirpreferred meanings are also preferred for the respective N-oxyls.

[0157] Also subject of the present invention is a polymerizablecomposition, comprising

[0158] a) at least one ethylenically unsaturated monomer or oligomer,and

[0159] b) a compound of formula (II) and c) a radical iniator X. capableof initiating polymerization of ethylenically unsaturated monomers.

[0160] The production of C-centered radicals X. is described, interalia, in Houben Weyl, Methoden der Organischen Chemie, Vol. E 19a, pages60-147. These methods can be applied in general analogy.

[0161] The source of radicals X. may be a bis-azo compound, a peroxideor a hydroperoxide.

[0162] Preferably, the source of radicals X. is2,2′-azobisisobutyronitrile, 2,2′-axobis(2-methyl-butyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride, 2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydrozyethyl]propionamide.Preferred peroxides and hydroperoxides are acetyl cyclohexane sulphonylperoxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate,t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate,bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoylperoxide, dioctanoyl peroxide, dilauroyl peroxide, bis (2-methylbenzoyl)peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoylperoxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide,t-butyl perisobutyrate, t-butyl permaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxy isopropyl carbonate, t-butyl perisononaoate, 2,5-dimethylhexane2,5-dibenzoate, t-butyl peracetate, t-amyl perbenzoate, t-butylperbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2bis (t-butylperoxy)propane, dicumyl peroxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide,3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxy isopropyl) benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane, di-t-butyl peroxide,2,5-dimethylhexyne-2,5di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl1,2,4,5-tetraoxa cyclononane, p-menthane hydroperoxide, pinanehydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumenehydroperoxide or t-butyl hydroperoxide.

[0163] These compounds are commercially available.

[0164] If more than one radical source is used, a mixture ofsubstitution patterns is obtainable.

[0165] The radical source is preferably present in an amount of from0.01 mol-% to 30 mol-%, more preferred in an amount of from 0.1 mol-% to20 mol-% and most preferred in an amount of from 0.5 mol-% to 10 mol-%based on the monomer or monomer mixture.

[0166] The molar ratio of the radical source to the compound of formulaeII may be from 1:10 to 10:1, preferably from 1:5 to 5:1 and morepreferably from 1:2 to 2:1.

[0167] Still another subject of the present invention is a process forpreparing an oligomer, a cooligomer, a polymer or a copolymer (block orrandom) by free radical polymerization of at least one ethylenicallyunsaturated monomer/oligomer, which comprises subjecting the abovecomposition to heat or actinic radiation. Definitions and preferencesfor the various substituents have already been mentioned with respect tothe initiator compounds. They apply also for the other subjects of theinvention including the preferences.

[0168] The initiators containing a structural element of formula I maybe prepared by known methods.

[0169] DE 26 21 841, U.S. Pat. No. 4,131,599 and DE 26 30 798 forexample describe the preparation of2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine and2,6-dipropyl-3-ethyl-2,6-dimethyl-4-oxo-piperidine, which areintermediates for the corresponding 1-oxo compounds.

[0170] Another method for the preparation of2,2-dimethyl-6,6-dialkyl-4-oxopiperidine is described by F. Asinger, M.Thiel, H. Baltz, Monatshefte für Chemie 88, 464 (1957) or by J. Bobbitttet al. in J. Org. Chem. 58, 4837 (1993).

[0171] The oxidation of the piperidine compound to 1-oxo-piperidinederivatives is well known in the art and for example described by L. B.Volodarsky, V. A. Reznikov, V. I. Ovcharenko in Synthetic Chemistry ofStable Nitroxides, CRC Press, Boca Raton 1994.

[0172] The nitroxides are then transformed into the NOR compounds offormula (I) or formulae (A) to (S) respectively, according to standardmethods. Examples for suitable reactions are described in T. J.Connolly, M. V. Baldovi, N. Mohtat, J. C. Scaiano.: Tet. Lett. 37, 4919(1996), I. Li, B. A. Howell et al.: Polym. Prepr. 36, 469 (1996), K.Matyjaszewski.: Macromol. Symp. 111, 47-61 (1996), P. Stipa, L. Greci,P. Carloni, E. Damiani.: Polym. Deg. Stab. 55, 323 (1997), Said OuladHammouch, J. M. Catala.: Macromol. Rapid Commun. 17, 149-154 (1996),Walchuk et al.: Polymer Preprints 39, 296 (1998) or Tan Ren, You-ChengLiu, Qing-Xiang Guo.: Bull. Chem. Soc. Jpn. 69, 2935 (1996).

[0173] The compounds containing a structural element of formula (I) areuseful compounds for the preparation of oligomers, cooligomers, polymersor copolymers. Hence a further subject of the invention is there use asinitiators for the polymerization of ethylenically unsaturated monomers.

[0174] The following examples illustrate the invention.

[0175] A) Preparation of Compounds

[0176] 2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine and2,6-dipropyl-3-ethyl-2,6-dimethyl-4-oxo-piperidine are preparedaccording to example 1 and 2 of DE 26 21 841.

EXAMPLE 1 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine

[0177] To a solution of 118.2 g (0.6 mol)2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine in 1000 ml ethanol 18.2 g(0.4 mol) sodium borohydride are added in portions and the temperatureis kept below 30° C. Subsequently the solution is stirred for 2 hours at50° C. Ethanol is distilled off, 500 ml water are added to the residuewhich is subsequently extracted several times with CH₂Cl₂. The extractis dried over Na₂SO₄ and the solution is filtered. After removing thesolvent 116 g (97%) 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidin areobtained as yellowish liquid.

[0178] Elemental analysis calculated for C₁₂H₂₅NO: C, 72.31%; H, 12.64%;N, 7.03%. Found: C, 71.44%; H, 12.71%; N, 6.87%.

Example 2 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1-oxyl

[0179] To a solution of 25.7 g (0.13 mol)2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine of example 1 in 120 mltetrahydrofurane a solution of a solution of 54.5 g (0.22 mol)m-chlor-perbenzoic acid (70%) in 230 ml tetrahydrofurane is droppwiseadded under stirring within 2 hours at 0° C. The red to brown solutionis stirred over night at room temperature and 500 ml hexane, are added.The solution is neutralized by shaking several times with 1 N NaHCO₃ andfinally with water. The solvent is evaporated and 27.0 g (97%)2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1oxyl are obtained asred liquid.

[0180] Elemental analysis calculated for C₁₂H₂₄NO₂: C, 67.25%; H,11.29%; N, 6.54%. Found: C, 67.10%; H, 11.42%; N, 6.68%.

EXAMPLE 3 2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine-1-oxyl

[0181] 2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine is prepared inanalogy to example 2 by oxidizing 16 g (0.08 mol)2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine with m-chlor-perbenzoicacid. 10 g 2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine-1-oxyl areobtained as red liquid.

[0182] Elemental analysis calculated for C₁₂H₂₂NO₂: C, 67.89%; H,10.44%; N, 6.60%. Found: C, 68.00%; H, 10.42%; N, 6.61%.

EXAMPLE 4 2,6-diethyl-2,3,6-trimethyl-4-propyloxypiperidine-1-oxyl

[0183] In a 200 ml three neck bottle 25.6 g (0.12 mol)2,6-diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl, 16 g (0.4 mol)sodium hydroxide, 3.86 g (0.012 mol) tetrabutyl-ammonium-bromide, 16 gwater and 30 ml toluene are added. The clear emulsion is heated up to60° C. and within 1 h 22.1 g (0.18 mol) propylbromide are dropwise addedunder stirring. The temperature is maintained for 12 h under stirring.The reaction mixture is cooled to room temperature, the water phase isseparated and the organic phase is washed neutral with water and driedover Na₂SO₄. The organic solvent is evaporated and the residue isdistilled over a short column. 21 g (68%)2,6-diethyl-2,3,6-trimethyl-4-propyloxy-piperidine-1-oxyl are obtainedas red liquid.

[0184] Elemental analysis calculated for C₁₅H₃₀NO₂: C, 70,27%; H,11.79%; N, 5.46%. Found: C, 70,26%; H, 11.90%; N, 5.34%.

EXAMPLE 5 2,6-dipropyl-2-ethyl-2,6-dimethyl4-oxypiperidine-1-oxyl

[0185] The title compound is prepared in analogy to example 2.5 g (0.021mol) 2,6-Dipropyl-2-ethyl-2,6-dimethyl-4-oxopiperidine are oxidized withm-chlor-perbenzoic acid. 5.5 g2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine-1-oxyl are obtained asred liquid.

[0186] Elemental analysis calculated for C₁₅H30NO₂: C, 70,27%; H,11.79%; N, 5.46%. Found: C, 72.31%; H, 11.02%; N, 5.07%.

BSP. 6 1-Benzyloxy-2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine (No. 101)

[0187] In a reactor suitable for conducting photo reactions 150 mltoluene, 4.4 g (0.02 mol)2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine-1-oxyl and 12.7 g (0.087mol) t-butylperoxide are added. The red solution is purged with nitrogenand subsequently irradiated with a mercury immersion lamp under nitrogenat 20-25° C. After 8 h the solution is colorless. The reaction mixtureis concentrated and the residue is subjected to column chromatography(silicagel, hexane-ethylacetate (9:1)). 4.8 g (77%)1-benzyloxy-2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine are isolated asyellowish liquid.

[0188] Elemental analysis calculated for C₁₉H₂₉NO₂: C, 75,20%; H, 9.63%;N, 4.61%. Found: C, 75.53%; H, 9.60%; N, 4.59%.

EXAMPLE 71-(1-phenylethoxy)-2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine (No.102)

[0189] The title compound is prepared in analogy to example 6. 8.5 g(0.04 mol) 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1-oxyl arereacted with t-butylperoxide in ethylbenzene. 10.5 g (82%)1-(1-phenylethoxy)-2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine areobtained as yellowish liquid.

[0190] Elemental analysis calculated for C₂₀H₃₃NO₂: C, 75.43%; H,10.30%; N, 4.35%. Found: C, 75.54%; H, 10.36%; N, 4.40%.

EXAMPLE 81-(1-phenylethoxy)-2,6-diethyl-2,3,6-trimethyl-4-propyloxypiperidine(No. 103)

[0191] The title compound is prepared in analogy to example 6. 5.63 g(0.022 mol) 2,6-diethyl-2,3,6-trimethyl-4-oxypropylpiperidine-1-oxyl arereacted with t-butylperoxide in ethylbenzene. 6.1 g (77%)1-(1-phenylethoxy)-2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine areobtained as yellowish liquid.

EXAMPLE 9 1-t-butyloxy-2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine (No.104)

[0192] The title compound is prepared in analogy to example 6. 4.77 g(0.022 mol) 2,6-diethyl-2,3,6-trimethyl-4-oxypropyl-piperidine-1-oxy and2.13 g (0.015 mol) 2,2′-azobis(2-methyl-propane) are reacted inethylbenzene. 1.15 g1-t-butyloxy-2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine are obtained asyellowish liquid.

[0193] Elemental analysis calculated for C₁₆H₃₁NO₂: C, 71.33%; H,11.60%; N, 5,20%. Found: C, 71,28%; H, 11.67%; N, 5.45%.

EXAMPLE 101-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine(No. 105)

[0194] The title compound is prepared in analogy to example 6. 5.0 g(0.021 mol) 2,6-Dipropyl-2-ethyl-2,6-dimethyl-4-oxopiperidine-1-oxyl andt-butylperoxide are reacted in ethylbenzene. 3.4 g (49%)1-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine areobtained as yellowish liquid.

[0195] Elemental analysis calculated for C₂₃H₃₇NO₂: C, 76.83%; H,10.37%; N, 3.90%. Found: C, 77.51%; H, 10.49%; N, 3.10%.

EXAMPLE 111-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-hydroxypiperidineNr.106)

[0196] The title compound is prepared in analogy to example 1. 3.1 g(0.009 mol)1-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine isreduced with sodium-borohydride in ethanol. 2.9 g (93%)1-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-hxdroxypiperidineare obtained as yellowish liquid.

[0197] Elemental analysis calculated for C₂₃H₃₉NO₂: C, 76.40%; H,10.87%; N, 3.87%. Found: C, 75.89%; H, 11.14%; N, 3.18%.

EXAMPLE 12 2,2,6-trimethyl-6-ethyl-piperidine

[0198] 33.8 g (0.2 mol) 2,2,6-trimethyl-6-ethyl-4-oxopiperidine, 14 g(0.28 mol) hydrazinhydrate and 13 g KOH in 80 ml diethylenglykol arestirred for 4 h at 160° C. Subsequently an additional amount of 30 g KOHdissolved in 30 ml water are added. 30 ml are distilled off. To theresidue two times 40 ml of water are added and removed by distillation.The combined distillates are saturated with solid K₂CO₃ and extractedwith methyl-tert.-butylether. From the extracts 6 g (19%)2,2,6-trimethyl-6-ethyl-piperidin are isolated by fractionateddistillation. A colorless liquid is obtained with a b.p. of 78-88° C./15mbar.

[0199]¹H-NMR (CDCl₃), δ ppm: 1.8-1.2 m (4×CH₂), 1.14 s (CH₃), 1.1 s(CH₃), 1.05 s (CH₃), 0.86 t (CH₃).

EXAMPLE 13 2,2,6-Trimethyl-6-ethyl-piperidine-1-oxyl

[0200] To a solution of 5.7 g (0.037 mol)2,2,6-trimethyl-6-ethyl-piperidine in 20 ml methanol, 0.07 g sodiumwolframate and 10 ml of 30% hydrogen peroxide are added. The mixture isstirred for 23 h at room temperature, diluted with a saturated NaClsolution and extracted with methyl-tert.-butylether. The combinedextracts are dried over MgSO₄ and concentrated under vacuum. The residueis subjected to column chromatography (silica gel, hexane-ethylacetate9:1). 4.6 g (73%) pure 2,2,6-trimethyl-6-ethyl-1-oxyl are isolated asred oil.

[0201] Elemental analysis calculated for C₁₀H₂₀NO: C, 70.54%; H, 11.84%;N, 8.23%. Found: C, 70.18%; H, 12.02%; N, 8.20%.

EXAMPLE 14 1-(Dimethylcyanomethyloxy)-2,2,6-trimethyl-6-ethyl-piperidine(No 107)

[0202] A solution of 2.8 g (0.016 mol)2,2,6-trimethyl-6-ethyl-piperidine-1-oxyl and 2.05 g (0.012 mol)azoisobutyronitril (AIBN) in 7 ml benzene are refluxed under argonatmosphere for 4 hours. Subsequently additional 1.5 g (0.009 mol) AIBNare added and the mixture is heated for one hour under argon. Thecolorless solution is concentrated under vacuum and subjected to columnchromatography (silica gel, hexane-ethylacetate 19:1). 1.63 g (42%)1-(dimethylcyanomethyloxy)-2,2,6-trimethyl-6-ethyl-piperidine areisolated as colorless oil which slowly crystallizes to a solid with m.p.of 41-52° C.

[0203] Elemental analysis calculated for C₁₄H₂₆N₂O: C, 70.54%; H,10.99%; N, 11.75%. Found: C, 70.49%; H, 10.71%; N, 11.60%.

EXAMPLE 15 2,2,6-Trimethyl-6-ethyl-4-hydroxypiperidine-1-oxyl

[0204] To a solution of 27.2 g (0.16 mol)2,2,6-trimethyl-6-ethyl-4-oxopiperidine in 100 ml methanol 3 g (0.08mol) sodium borohydride are added in portions. The temperature is keptbelow 30° C. After stirring over night 55 ml (0.64 mol) of 35% hydrogenperoxide, 0.5 g sodium tungstate, 40 ml of 20% sodium carbonate andadditional 60 ml methanol are added. After stirring for another 20 h atroom temperature the reaction mixture is filtered, diluted with 100 mlsaturated NaCl solution and subsequently extracted 3-times withhexane-methyl-tert.-butylether (1:1). The combined extracts are driedover MgSO₄ and concentrated under vacuum. The residue is subjected tocolumn chromatography (silica gel, hexane-ethylacetate 1:1). 12.5 g(42%) pure 2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine-1-oxyl areisolated as red oil

[0205] Elemental analysis calculated for C₁₀H₂₀NO₂: C, 64.48%; H,10.82%; N, 7.52%. Found: C, 63.73%; H, 10.87%; N, 7.24%.

EXAMPLE 161-(dimethylcyanomethyloxy)-2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine(No. 108)

[0206] A solution of 2.0 g (0.0107 mol)2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine-1-oxyl and 2.65 g (0.016mol) azoisobutyronitril (AIBN) in 8 ml benzene is refluxed under argonfor 30 minutes. The colorless solution is concentrated under vacuum andsubjected to column chromatography (silica gel, hexane-ethylacetate2:1). The combined fractions are recrystallized from hexane. 2.0 g (73%)1-(dimethylcyanomethyloxy)-2,2,6-trimethyl-6-ethyl-4-4-hydroxypoperidinewith a m.p. of 48-60° C. are isolated.

[0207] Elemental analysis calculated for C₁₄H₂₆N₂O₂: C, 66.1 1%; H,10.30%; N, 11.01 %. Found: C, 65.77%; H, 10.49%; N, 11.04%.

EXAMPLE 171-(1-phenylethoxy)-2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine (No 109)

[0208] 3.1 g (0.0166 mol)2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine-1-oxyl, 2.2 g (0.0153 mol)Copper (I) bromide and 4.1 g (0.0153 mol)4,4′-di-tert.-butyl-[2,2′]bipyridinyl are added to 20 ml benzene. Thesolution is purged with argon and evacuated for several times to removethe oxygen from the solution. With a syringe 2.79 g (0.0151 mol)1-phenylethylbromide are added. The mixture is stirred for 21 h at roomtemperature. The green suspension is filtered over Cellit and thefiltrate is removed from benzene under vacuum. The residue is subjectedto column chromatography (silica gel, hexane-ethylacetate 4:1). 2.18 g(45%) 1-(1-phenylethoxy)-2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine areobtained as colorless oil. Recrystallization from hexane results incrystals of a m.p. of 58-69° C.

[0209]¹H-NMR (CDCl₃), δ ppm: 7.3 m 5 H (ArH), 4.75 m 1H (OCH(CH₃)Ph),3.88 m 1H (CHOH), 2.1-0.5 m 21H (4×CH₃, 1×C₂H₅, CH₂COCH₂).

EXAMPLE 18 2,2,6-Trimethyl-6-isopropyl-4-oxopiperidine

[0210] The title compound is prepared in analogy to F. Asinger, M.Thiel, H. Baltz.: Monatshefte für Chemie 88, 464 (1957) frommesityloxide, methylisopropylketone and ammonia. A colorless liquid isobtained.

[0211]¹H-NMR (CDCl₃), δ ppm: 2.25 m 4H (CH₂COCH₂), 1.64 m 1H (CH(CH₃)₂),1.24 s (CH3), 1.21 s (CH3), 1.07 s (CH3), 0.91 dd 6H (CH(CH₃)₂).

EXAMPLE 19 2,2,6-trimethyl-6-isopropyl-4oxopiperidine-1-oxyl

[0212] 2.75 g (0.015 mol) 2,2,6-trimethyl-6-isopropyl-4-oxopiperidine,0.08 g sodium wolframate, 0.2 g sodium carbonate, 10 ml of 30% hydrogenperoxide and 10 ml methanol are stirred for 22 h at room temperature. 20ml saturated NaCl solution are added and the mixture is extracted3-times with hexane-methyl-tert.-butylether (1:1). The combined extractsare dried over MgSO₄ and concentrated under vacuum. The residue issubjected to column chromatography (silica gel, hexane-ethylacetate4:1). 1.8 g (60%) pure 2,2,6-trimethyl-6-isopropyl-4-oxopiperidine areisolated as red oil. Recrystallization from pentane results in a solidof a m.p. of 47-53° C.

[0213] Elemental analysis calculated for C₁₁H₂₀NO₂: C, 66.63%; H,10.17%; N, 7.06%. Found: C, 66.42%; H, 10.19%; N, 7.10%.

EXAMPLE 201-(dimethylcyanomethyl)-2,2,6-trimethyl-6-isopropyl-4-oxopiperidine (No111)

[0214] A solution of 1.0 g (0.005 mol)2,2,6-trimethyl-6-isopropyl-4-oxopiperidine-1-oxyl and 1.6 g (0.01 mol)azoisobutyronitril (AIBN) in 5 ml benzene are refluxed under argon for30 minutes. The colorless solution is concentrated under vacuum andsubjected to column chromatography (silica gel, hexane-ethylacetate9:1). The combined fractions are recrystallized from hexane. 0.55 g(41%)1-(dimethylcyanomethyloxy)-2,2,6-trimethyl-6-isopropyl-4-oxopiperidinewith a m.p. of 32-44° C. are obtained.

[0215]¹H-NMR (CDCl₃), δ ppm: 2.5 m 4H (CH₂COCH₂), 2.15 m 1H (CH(CH₃)₂),1.69 s 6H ((CH₃)₂CCN), 1.37 s (CH3), 1.33 s (CH3), 1.26 s (CH3), 0.91 dd6H (CH(CH₃)₂).

EXAMPLE 21 2,2-dimethyl-6,6-diethyl4-hydroxypiperidine

[0216] To a solution of 15.8 g (0.086 mol)2,2-dimethyl-6,6-diethyl-4-oxopiperidine in 50 ml methanol 2.2 g (0.06M) sodium borohydride are added in portions. The temperature is keptbelow 30° C. After stirring over night methanol is removed under vacuumand the residue is diluted with 20 ml 2N-NaOH. The solution is extractedwith ethylacetate. The combined extracts are washed with saturated NaClsolution, dried over MgSO₄ and dried under vacuum at 60° C./50 mbaruntil a constant weight is achieved. 15.8 g (99%)2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine are obtained as yellowishoil.

EXAMPLE 22 2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine-1-oxyl

[0217] 15.85 g (0.085 mol) 2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine,0.25 g sodium wolframate, 1 g sodium carbonate, 26 ml of 35% hydrogenperoxide and 45 ml methanol are stirred for 28 h at room temperature.100 ml saturated NaCl solution are added and the mixture is extracted3-times with hexane-methyl-tert.-butylether (1:1). The combined extractsare dried over MgSO₄ and concentrated under vacuum. The residue issubjected to column chromatography (silica gel, hexane-ethylacetate2:1). 8.55 g (50%) pure2,2-Dimethyl-6,6-diethyl-4-hydroxypiperidine-1-oxyl are isolated as redoil.

EXAMPLE 23 1(1-phenylethoxy)-2,2dimethyl-6,6-diethyl-4-hydroxypiperidine(No 110)

[0218] 2.0 g (0.01 mol)2,2-dimethyl-6,6-diethyl-4-hydroxypipenidine-1-oxyl, 1.43 g (0.01 mol)Copper (I) bromide and 1.56 g (0.01 mol)4,4′-di-tert.-butyl-[2,2′]bipyridinyl are added to 20 ml benzene. Thesolution is purged with argon and evacuated for several times to removethe oxygen from the solution. With a syringe 1.85 g (0.01 mol)1-phenylethylbromid are added. The mixture is stirred for 16 h at roomtemperature. Additional 0.3 g (0.002 mol Copper (I) are added underargon and the solution is stirred for another 23 h. The green suspensionis filtered over Cellit and the filtrate is removed from benzene undervacuum. The residue is subjected to column chromatography (silica gel,hexane-ethylacetate 3:1). After recrystallization from hexane 0.8 g1-(1-phenylethoxy)-2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine with am.p. of 84-86° C. are obtained. Elemental analysis calculated forC₁₉H₃₁NO₂: C 74.71%; H 10.23%; N 4.59%. Found: C 74.77%; H 10.39%; N4.55%.

EXAMPLE 241-(1-phenylethoxy)-2,3,6-trimethyl-2,6-diethyl-4-oxopiperidine (Nr 112)

[0219] The title compound is prepared in analogy to example 6. 4.7 g(0.022 mol) 2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine-1-oxyl arereacted with t-butylperoxide in ethylbenzene. 5.0 g (71%)1-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine areobtained a yellowish liquid.

[0220] Elemental analysis calculated for C₂₂H₃₁NO₂: C, 75.67%; H, 9.84%;N, 4.41%. Found: C, 75.60%; H, 9.77%; N, 4.34%.

EXAMPLE 251-(1-phenylethoxy)-2,2-dimethyl-6,6-diethyl-4-benzoyloxypiperidine (No113)

[0221] A) 2,2-Dimethyl-6,6-diethyl-4-benzoyloxypiperidine-1-oxyl To astirred solution of 6.05 g (0.03 mol) of2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine-1-oxyl in 20 ml of pyridineare slowly and under cooling with ice added 3.8 ml (0.032 mol) ofbenzoylchloride. Afterwards, the mixture is stirred for 3.5 h at roomtemperature, then diluted with 200 ml of water and extracted twice with50 ml of hexane. The combined extracts are washed with water, dried overMgSO₄ and evaporated in vacuo to give 9.1 g of2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine-1-oxyl as a thick, red oil.

[0222] Elemental analysis calculated for C₁₈H₂₆NO₃: C, 71.02%; H, 8.61%;N, 4.60%. Found: C, 70.96%; H, 8.76%; N, 4.53%.

[0223] B) 3.04 g (0.01 mol) of2,2-dimethyl-6,6-diethyl-4-benzoyloxypiperidine-1-oxyl and 7.37 ml oft-butylperoxide in 200 ml of ethylbenzene are photolyzed as described inexample 6 to afford 5.5 g of1-(1-phenylethoxy)-2,2-dimethyl-6,6-diethyl-4-benzoyloxypiperidine as athick colorless oil.

[0224]¹H-NMR (CDCl₃), d ppm: 0.5-2.0 m (23H), 4.74 m (1H), 5.2 m (1H),7.2-7.6 m 8H) 8.00-8.03 d(2 H).

EXAMPLE 26 2,6-diethyl-2,3,6-trimethyl-4-lauroyloxypiperidine-1-oxyl

[0225] To a stirred solution of 21,4 g (0.1 mol) of2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1-oxyl in 15 mltriethylamine and 70 ml toluene are slowly and under cooling with iceadded 19.9 g (0.091 mol) of lauroyl chloride. Afterwards, the mixture isstirred for 6 hrs at room temperature, then diluted with 200 ml of waterand extracted twice with 100 ml of toluene. The combined extracts arewashed with water, dried over MgSO₄ and evaporated in vacuo and theresidue is subjected to column chromatography (silicagel,hexane-ethylacetate (5:1)). 25.2 g (64%)2,6-diethyl-2,3,6-trimethyl-4-lauroyloxypiperidine-1-oxyl are isolatedas a red oil.

[0226] Elemental analysis calculated for C₂₄H₄₆NO₃: C, 72.67%; H,11.69%; N, 3.53%. Found: C, 72.39%; H, 11.60%; N, 3.30%.

EXAMPLE 27 2,6-diethyl-2,3,6-trimethyl-4-stearoyloxypiperidine-1-oxyl

[0227] To a stirred solution of 5 g (0.023 mol) of2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1-oxyl in 5 mltriethylamine and 40 ml toluene are slowly and under cooling with iceadded 7.1 g (0.021 mol) of stearyl chloride. Afterwards, the mixture isstirred for 6 hrs at room temperature, then diluted with 100 ml of waterand extracted twice with 50 ml of toluene. The combined extracts arewashed with water, dried over MgSO₄ and evaporated in vacuo and theresidue is subjected to column chromatography (silicagel,hexane-ethylacetate (5:1)). 5,8 g (52%)2,6-diethyl-2,3,6-trimethyl-4-stearoyloxypiperidine-1-oxyl are isolatedas a red oil.

[0228] Elemental analysis calculated for C₃₀H₅₈NO₃: C, 74.94%; H,12.16%; N, 2.91%. Found: C, 74.96%; H, 12.00%; N, 2.69%.

EXAMPLE 28 2,2-dimethyl-6,6-diethyl-4-lauroyloxypiperidine-1-oxyl

[0229] To a stirred solution of 2,0 g (0.01 mol) of2,2-dimethyl-6,6-diaethyl-4-hydroxypiperidine-1-oxyl in 2 mltriethylamine and 25 ml toluene are slowly and under cooling with iceadded 2.0 g (0.0091 mol) of lauroyl chloride. Afterwards, the mixture isstirred for 6 hrs at room temperature, then diluted with 50 ml of waterand extracted twice with 25 ml of toluene. The combined extracts arewashed with water, dried over MgSO₄ and evaporated in vacuo and theresidue is subjected to column chromatography (silicagel,hexane-ethylacetate (5:1)). 1.8 g (48%)2,2-dimethyl-6,6-diethyl-4-lauroyloxypiperidine-1-oxyl are isolated as ared oil.

[0230] Elemental analysis calculated for C₂₃H₄₄NO₃: C, 72.20%; H,11.60%; N, 3.66%. Found: C, 72.01%; H, 11.61%; N, 3.48%.

EXAMPLE 29 2,2-dimethyl-6,6-diethyl-4-stearoyloxypiperidine-1-oxyl

[0231] To a stirred solution of 5.0 g (0.025 mol) of2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine-1-oxyl in 5 mltriethylamine and 40 ml toluene are slowly and under cooling with iceadded 7.9 g (0.023 mol) of stearoyl chloride. Afterwards, the mixture isstirred for 6 hrs at room temperature, then diluted with 100 ml of waterand extracted twice with 50 ml of toluene. The combined extracts arewashed with water, dried over MgSO₄ and evaporated in vacuo and theresidue is subjected to column chromatography (silicagel,hexane-ethylacetate (5:1)). 6.15 g (52%)2,2-dimethyl-6,6-diaethyl-4-stearoyloxypiperidine-1-oxyl are isolated asa red oil.

[0232] Elemental analysis calculated for C₂₉H₅₆NO₃: C, 74.62%; H,12.09%; N, 3.00%. Found: C, 74.47%; H, 12.03%; N, 2.99%.

EXAMPLE 30 2,6-diethyl-2,3,6-trimethyl-4-propoxypiperidine-1-oxyl

[0233] To a stirred solution of 128 g (0.6 mol) of2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1-oxyl, 80 g NaOH, 80 gwater, 19.3 g tetrabutylammonium bromide and 240 ml toluene are slowlyadded at 50° C. 111 g (0.9 mol) of propylbromide. Afterwards, themixture is stirred for 10 hrs at 50° C., then diluted with 200 ml ofwater and the organic phase is separated . The organic phase is washedwith water, dried over MgSO₄ and evaporated in vacuo. The raw product ispurified by destiliation. 81 g (54%)2,6-diethyl-2,3,6-trimethyl-4-propoxypiperidine-1-oxyl are isolated as ared oil.

[0234] Elemental analysis calculated for C₁₅H₃₀NO₂: C, 70.27%; H,11.79%; N, 5.46%. Found: C, 70.26%; H, 11.88%; N, 5.40%.

[0235] The N—O—X compounds prepared, are listed in Table 1 TABLE 1 No.Compound 101

102

103

104

105

106

107

108

109

110

111

112

113

[0236] B) Polymerizations Using Compounds of Table 1 or their N—.Precursors as Initiators

[0237] General remarks:

[0238] Solvents and monomers are distilled over a Vigreux column underargon atmosphere or under vacuum, shortly before being used.

[0239] To remove oxygen all polymerization reaction mixtures are flushedbefore polymerization with argon and evacuated under vaccum applying afreeze-thaw cycle. The reaction mixtures are then polymerized underargon atmosphere.

[0240] At the start of the polymerization reaction, all startingmaterials are homogeneously dissolved.

[0241] Conversion is determined by removing unreacted monomers from thepolymer at 80° C. and 0.002 torr for 30 minutes, weighing the remainingpolymer and subtract the weight of the initiator.

[0242] Characterization of the polymers is carried out by MALDI-MS(Matrix Assisted Laser Desorption Ionization Mass Spectrometry) and/orGPC (Gel Permeation Chromatography).

[0243] MALDI-MS: Measurements are performed on a linear TOF (Time OfFlight) MALDI-MS LDI-1700 Linear Scientific Inc., Reno, USA. The matrixis 2,5-dihydroxybenzoic acid and the laser wavelength is 337 nm.

[0244] GPC: Is performed using RHEOS 4000 of FLUX INSTRUMENTS.Tetrahydrofurane (THF) is used as a solvent and is pumped at 1 ml/min.Two chromatography columns are put in series: type Plgel 5 μm mixed-C ofPOLYMER INSTRUMENTS, Shropshire, UK. Measurements are performed at 40°C. The columns are calibrated with low polydispersity polystyreneshaving Mn from 200 to 2 000 000 Dalton. Detection is carried out using aRI-Dector ERC-7515A of ERCATECH AG at 30° C.

[0245] B) Polymerizations with Acrylates

[0246] B1-B10 Homopolymers

Example B1

[0247] Polymerization of n-butylacrylate Using Compound 101

[0248] In a 50 ml three neck flask, equipped with thermometer, coolerand magnetic stirrer, 710 mg (2.34 mmol) of compound 101 and 20 g (156mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 145° C. and polymerization is carriedout during 5 h. The reaction mixture is then cooled to 80° C. Theremaining monomer is removed by evaporation under high vacuum. 19.3 g(93%) of the initial monomer have reacted. A clear colorless viscousfluid is obtained.

[0249] GPC: Mn=12000, Mw=21300 , Polydispersity (PD)=1.77

Example B2

[0250] Polymerization of n-butylacrylate Using Compound 102

[0251] In a 50 ml three neck flask, equipped with thermometer, coolerand magnetic stirrer, 743 mg (2.34 mmol) of compound 102 and 20 g (156mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 145° C. and polymerization is carriedout during 5 h. The reaction mixture is then cooled to 80° C. Theremaining monomer is removed by evaporation under high vacuum. 16.8 g(80%) of the initial monomer have reacted. A clear colorless viscousfluid is obtained.

[0252] GPC: Mn=7500, Mw=8700, Polydispersity (PD)=1.16

Example B3

[0253] Polymerization of n-butylacrylate Using Compound 103

[0254] In a 50 ml three neck flask, equipped with thermometer, coolerand magnetic stirrer, 4.51 g (12.5 mmol) of compound 103 and 16 g (125mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 145° C. and polymerization is carriedout during 5 h. The reaction mixture is then cooled to 80° C. Theremaining monomer is removed by evaporation under high vacuum. 14.9 g(65%) of the initial monomer have reacted. A clear orange viscous fluidis obtained. The raw product is subjected to column chromatography(silica gel, hexane-ethylacetate 1:4) and 10.4 g of a colorless viscousliquid is obtained.

[0255] GPC: Mn=1550, Mw=1900, Polydispersity (PD)=1.22

Example B4

[0256] Polymerization of n-butylacrylate Using Compound 104

[0257] In a 50 ml three neck flask, equipped with thermometer, coolerand magnetic stirrer, 473 mg (1.76 mmol) Nr 104 and 15 g (117 mmol) ofn-butylacrylate are mixed and degased. The clear solution obtained isheated under argon to 14520 C. and polymerization is carried out during5 h. The reaction mixture is then cooled to 80° C. The remaining monomeris removed by evaporation under high vacuum. 1.65 g (11%) of the initialmonomer have reacted. A clear slight orange viscous fluid is obtained.

Example B5

[0258] Polymerization of n-butylacrylate Using Compound 106

[0259] In a 50 ml three neck flask, equipped with thermometer, coolerand magnetic stirrer, 844 mg (2.34 mmol) of compound 106 and 20 g (156mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 145° C. and polymerization is carriedout during 2 h. The reaction mixture is then cooled to 80° C. Theremaining monomer is removed by evaporation under high vacuum. 16.8 g(80%) of the initial monomer have reacted. A clear colorless viscousfluid is obtained. After 2 h 15.2 g (76%) of the initial monomer havereacted. A clear colorless viscous fluid is obtained.

[0260] GPC: Mn=6550, Mw=8100, Polydispersity (PD)=1,24

Example B6

[0261] Polymerization of n-butylacrylate Using Compound 110

[0262] In a 50 ml three neck flask, equipped with thermometer, coolerand magnetic stirrer, 357 mg (1.2 mmol) of compound 110 and 10 g (78mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 145° C. and polymerization is carriedout during 5 h. The reaction mixture is then cooled to 80° C. Theremaining monomer is removed by evaporation under high vacuum. 7.6 g(76%) of the initial monomer have reacted. A clear slightly orangeviscous fluid is obtained.

[0263] GPC: Mn=6100, Mw=7500, Polydispersität (PD)=1.2

Example B7

[0264] Polymerization of n-butylacrylate Using Compound 112

[0265] In a 50 ml three neck flask, equipped with thermometer, coolerand magnetic stirrer, 743 mg (2.34 mmol) of compound 112 and 20 g (156mmol) of n-butylacrylate are mixed and degased. The clear solutionobtained is heated under argon to 145° C. and polymerization is carriedout during 5 h. The reaction mixture is then cooled to 60° C. Theremaining monomer is removed by evaporation under high vacuum. 16 g(80%) of the initial monomer have reacted. A clear slightly orangeviscous fluid is obtained.

[0266] GPC: Mn=7500, Mw=8700, Polydispersität (PD)=1.2

[0267] MALDI-TOF: Mn=6400, Mw=7700, Polydispersität (PD)=1.2

Example B8

[0268] Polymerization of Dimethylaminoethylacrylate Using Compound 102

[0269] A 50 ml round-boftom three necked flask, equipped withthermometer, condenser and magnetic stirrer is charged with 0.268 g (0.8mmol) of compound 102 and 8 g (56 mmol) of dimethylaminoethylacrylateand degassed. The clear yellow solution is then heated to 145° C. underargon. The mixture is stirred for 1 hour at 145° C. and then cooled to60° C. and the remaining monomer is evaporated under high vacuum. 5.6 g(70%) of a brown viscous polymer are obtained.

[0270] GPC: Mn=2300, Mw=3700, Polydispersity=1.6

Example B9

[0271] Polymerization of Dimethylaminoethylacrylate Using Compound 110

[0272] A 50 ml round-bottom three necked flask, equipped withthermometer, condenser and magnetic stirrer is charged with 0.256 g (0.8mmol) of compound 110 and 8 g (56 mmol) of dimethylaminoethylacrylateand degassed. The clear yellow solution is then heated to 145° C. underargon. The mixture is stirred for 1 hour at 145° C. and then cooled to60° C. and the remaining monomer is evaporated under high vacuum. 5.7 g(72%) of a brown viscous polymer are obtained.

[0273] GPC: Mn=2100, Mw=3300, Polydispersity=1.6

Example B10

[0274] Polymerization of t-butylacrylate Using Compound 110

[0275] A round-bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 0.178 g (0.6 mmol) ofcompound 110 and 5 g (39 mmol) of t-butylacrylate and degassed. Theclear solution is then heated to 145° C. under argon. The mixture isstirred for 3 hour at 145° C. and then cooled to 60° C. and theremaining monomer is evaporated under high vacuum. 1 g (20%) of a brownviscous polymer are obtained.

[0276] GPC: Mn=1800, Mw=2900, Polydispersity=1.6

[0277] B11-B15 Blockcopolymers

Example B11

[0278] Copolymerization of poly-n-butylacrylate Made with Compound 102with n-butylacrylate

[0279] A round-bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 12 g (93 mmol)n-butylacrylate and 12.5 g of poly-n-butylacrylate (made with compound102, Mn=7500, PD=1.2) and degassed. The solution is then heated to 145°C. under argon. The mixture is stirred for 5 hour at 145° C. and thencooled to 60° C. and the remaining monomer is evaporated under highvacuum. 20% of the additional monomer is reacted and an orange viscousliquid is obtained.

[0280] GPC: Mn=8500, Mw=11400, Polydispersity=1.4

Example B12

[0281] Copolymerization of poly-n-butylacrylate Made with Compound 102with dimethylaminoethylmethacrylate

[0282] A round-bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 14.5 g (93 mmol)dimethylaminoethylmethacrylate and 12.5 g of poly-n-butylacrylate (madewith compound 102, Mn=7500, PD=1.2) and degassed. The solution is thenheated to 145° C. under argon. The mixture is stirred for 5 hour at 145°C. and then cooled to 60° C. and the remaining monomer is evaporatedunder high vacuum. 10% of the additional monomer is reacted and anorange viscous liquid is obtained.

[0283] GPC: Mn=8200, Mw=13200, Polydispersity =1.6

Example B13

[0284] Copolymerization of Poly-n-butylacrylate Made with Compound 110with n-butylacrylate

[0285] A round-bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 11 g (86 mmol)n-butylacrylate and 11.5 g of poly-n-butylacrylate (made with compound110, Mn=5600, PD=1.3) and degassed. The solution is then heated to 145°C. under argon. The mixture is stirred for 5 hour at 145° C. and thencooled to 60° C. and the remaining monomer is evaporated under highvacuum. 10% of the additional monomer is reacted and an orange viscousliquid is obtained.

[0286] GPC: Mn=6500, Mw=8500, Polydispersity=1.3

Example B14

[0287] Copolymerization of poly-n-butylacrylate Made with Compound 110with dimethylaminoethylmethacrylate (50/50)

[0288] A round-bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 5 g (37 mmol)dimethylaminoethylmethacrylate and 5 g of poly-n-butylacrylate (madewith compound 110, Mn=5600, PD=1.3) and degassed. The solution is thenheated to 145° C. under argon. The mixture is stirred for 3 hour at 145°C. and then cooled to 60° C. and the remaining monomer is evaporatedunder high vacuum. 20% of the additional monomer is reacted and anorange viscous liquid is obtained.

[0289] GPC: Mn=5500, Mw=7400, Polydispersity=1.3

Example B15

[0290] Copolymerization of poly-n-butylacrylate Made with Compound 110with dimethylaminoethylmethacrylate (20/80)

[0291] A round-bottom three necked flask, equipped with thermometer,condenser and magnetic stirrer is charged with 18 g (115 mmol)dimethylaminoethylmethacrylate and 4 g of poly-n-butylacrylate (madewith compound 110, Mn=5600, PD=1.3) and degassed. The solution is thenheated to 145° C. under argon. The mixture is stirred for 3 hour at 145°C. and then cooled to 60° C. and the remaining monomer is evaporatedunder high vacuum. 30% of the additional monomer is reacted and anorange viscous liquid is obtained.

[0292] GPC: Mn=10000, Mw=17700, Polydispersity=1.8

[0293] C) Polymerizations with Styrene Homopolymerization with NOR

Example C1

[0294] Polymerization of Styrene Using compound 102

[0295] 50 ml of styrene and 0.087 mol/l of compound 102 are heated underargon for 6 hrs to 130° C. The reaction mixture is then cooled to 80° C.and the remaining monomer is removed by evaporation under high vacuum.33 g (66%) of a colorless polymer are obtained.

[0296] GPC: Mn=8000, Mw=9100, Polydispersity=1.14

Example C2

[0297] Polymerization of Styrene Using Compound 102

[0298] 50 ml of styrene and 0.0087 mol/l of compound 102 are heatedunder argon for 6 hrs to 130° C. The reaction mixture is then cooled to80° C. and the remaining monomer is removed by evaporation under highvacuum. 37.5 g (75%) of a colorless polymer are obtained.

[0299] GPC: Mn=48400, Mw=67200, Polydispersity=1.39

[0300] Homopolymerization with nitroxide+benzoylperoxide (BPO)

Example C3

[0301] Polymerization of Styrene Using Nitroxide from Example A2+(BPO)

[0302] 50 ml of styrene, 0.0087 mol/l nitroxide (from Example 2) and0.0069 mol/l BPO are heated under argon for 6 hrs to 120° C. Thereaction mixture is then cooled to 80° C. and the remaining monomer isremoved by evaporation under high vacuum. 27.5 g (55%) of a colorlesspolymer are obtained.

[0303] GPC: Mn=48100, Mw=61500, Polydispersity=1.28

Example C4

[0304] Polymerization of Styrene Using Nitroxide from Example A2+BPO

[0305] 100 ml of styrene, 0.087 mol/l nitroxide (from Example 2) and0.069 mol/l BPO are heated under argon for 6 hrs to 120° C. The reactionmixture is then cooled to 80° C. and the remaining monomer is removed byevaporation under high vacuum. 35 g (35%) of a colorless polymer areobtained.

[0306] GPC: Mn=6200, Mw=7000, Polydispersity=1.13

Example C5

[0307] Polymerization of Styrene Using Nitroxide from Example A26+BPO

[0308] 50 ml of styrene, 0.087 mol/l nitroxide (from Example 26) and0.069 mol/I BPO are heated under argon for 6 hrs to 130° C. The reactionmixture is then cooled to 80° C. and the remaining monomer is removed byevaporation under high vacuum. 39 g (78%) of a colorless polymer areobtained.

[0309] GPC: Mn=9000, Mw=10600, Polydispersity=1.18

Example C6

[0310] Polymerization of Styrene Using Nitroxide from Example A26+BPO

[0311] 50 ml of styrene, 0.0087 mol/l nitroxide (from Example 26) and0.0069 mol/l BPO are heated under argon for 6 hrs to 130° C. Thereaction mixture is then cooled to 80° C. and the remaining monomer isremoved by evaporation under high vacuum. 40 g (80%) of a colorlesspolymer are obtained.

[0312] GPC: Mn=50600, Mw=72000, Polydispersity=1.43

Example C7

[0313] Copolymerization Styrene/Styrene

[0314] 5 ml of polystyrene from Example 4 and 5 g of styrene are heatedunder argon for 6 hrs to 130° C. The reaction mixture is then cooled to80° C. and the remaining monomer is removed by evaporation under highvacuum. A colorless polymer is obtained.

[0315] GPC: Mn=9500, Mw=12000, Polydispersity=1.27

Example C8

[0316] Copolymerization Styrene/n-Butylacrylate

[0317] 5 ml of polystyrene from Example C4 and 5 g of n-butylacrylateare heated under argon for 6 hrs to 130° C. The reaction mixture is thencooled to 80° C. and the remaining monomer is removed by evaporationunder high vacuum. A colorless polymer is obtained.

[0318] GPC: Mn=8200, Mw=9700, Polydispersity=1.18

1. A 1-alkoxy-polyalkyl-piperidine derivative containing a structuralelement of formula (I)

wherein G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl with the provisothat at least one is not methyl or G₁ and G₂ or G₃ and G₄, or G₁ and G₂and G₃ and G₄ together form a C₅-C₁₂cycloalkyl group; G₅, G₆independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or a groupCOOC₁-C₁₈alkyl and X represents a group such that the free radical X.derived from X is capable of initiating polymerization of ethylenicallyunsaturated monomers, with the proviso that compounds A1 and A2 areexcluded


2. A compound or mixture of compounds of any of formulae A to Saccording to claim 1

wherein G₁, G₂, G₃ and G₄ are independently alkyl of 1 to 4 carbonatoms, or G₁ and G₂ together and G₃ and G₄ together, or G₁ and G₂together or G₃ and G₄ together are pentamethylene; G₅ and G₆ areindependently hydrogen or C₁-C₄ alkyl; R, if m is 1, is hydrogen,C₁-C₁₈alkyl which is uninterrupted or C₂-C₁₈alkyl which is interruptedby one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalentradical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, ofa cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or anα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms, where eachcarboxylic acid can be substituted in the aliphatic, cycloaliphatic oraromatic moiety by 1 to 3 —COOZ₁₂ groups, in which Z₁₂ is H,C₁-C₂₀alkyl, C₃-C₁₂alkenyl, C₅-C₇cycloalkyl, phenyl or benzyl; or R is amonovalent radical of a carbamic acid or phosphorus-containing acid or amonovalent silyl radical; R, if m is 2, is C₂-C₁₂alkylene,C₄-C₁₂alkenylene, xylylene, a divalent radical of an aliphaticdicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic oraromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic,cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms,where each dicarboxylic acid may be substituted in the aliphatic,cycloaliphatic or aromatic moiety by one or two —COOZ₁₂ groups; or R isa divalent radical of a phosphorus-containing acid or a divalent silylradical; R, if m is 3, is a trivalent radical of an aliphatic,cycloaliphatic or aromatic tricarboxylic acid, which may be substitutedin the aliphatic, cycloaliphatic or aromatic moiety by —COOZ₁₂, of anaromatic tricarbamic acid or of a phosphorus-containing acid, or is atrivalent silyl radical, R, if m is 4, is a tetravalent radical of analiphatic, cycloaliphatic or aromatic tetracarboxylic acid; p is 1, 2 or3, R₁ is C₁-C₁₂alkyl, C₅-C₇cycloalkyl, C₇-C₈aralkyl, C₂-C₁₈alkanoyl,C₃-C₅alkenoyl or benzoyl; when p is 1, R₂ is C₁-C₁₈alkyl,C₅-C₇cycloalkyl, C₂-C₈alkenyl unsubstituted or substituted by a cyano,carbonyl or carbamide group, or is glycidyl, a group of the formula—CH₂CH(OH)—Z or of the formula —CO—Z— or —CONH—Z wherein Z is hydrogen,methyl or phenyl; or when p is 2, R₂ is C₂-C₁₂alkylene, C₆-C₁₂-arylene,xylylene, a —CH₂CH(OH)CH₂—O—B—O—CH₂CH(OH)CH₂— group, wherein B isC₂-C₁₀alkylene, C₆-C₁₅arylene or C₆-C₁₂cycloalkylene; or, provided thatR₁ is not alkanoyl, alkenoyl or benzoyl, R₂ can also be a divalent acylradical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid ordicarbamic acid, or can be the group —CO—; or R₁ and R₂ together when pis 1 can be the cyclic acyl radical of an aliphatic or aromatic 1,2- or1,3-dicarboxylic acid; or R₂ is a group

where T₇ and T₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, or T₇ and T₈ together are alkylene of 4 to 6 carbon atoms or3-oxapentamethylene; when p is 3, R₂ is 2,4,6-triazinyl; when n is 1, R₃is C₂-C₈alkylene or hydroxyalkylene or C₄-C₂₂acyloxyalkylene; or when nis 2, R₃ is (—CH₂)₂C(CH₂—)₂; when n is 1, R₄ is hydrogen, C₁-C₁₂alkyl,C₃-C₅alkenyl, C₇-C₉aralkyl, C₅-C₇cycloalkyl, C₂-C₄hydroxyalkyl,C₂-C₆-alkoxyalkyl, C₆-C₁₀-aryl, glycidyl, a group of formula—(CH₂)_(m)—COO—Q or of the formula —(CH₂)_(m)—O—CO—Q wherein m is 1 or 2and Q is C₁-C₄-alkyl or phenyl; or when n is 2, R₄ is C₂-C₁₂alkylene,C₆-C₁₂-arylene, a group —CH₂CH(OH)CH₂—O—D—O—CH₂CH(OH)CH₂— wherein D isC₂-C₁₀alkylene, C₆-C₁₅arylene or C₆-C₁₂cycloalkylene, or a group—CH₂CH(OZ₁)CH₂—(OCH₂CH(OZ₁)CH₂)₂— wherein Z₁ is hydrogen, C₁-C₁₈alkyl,allyl, benzyl, C₂-C₁₂alkanoyl or benzoyl; R₅ is hydrogen, C₁-C₁₂alkyl,allyl, benzyl, glycidyl or C₂-C₆alkoxyalkyl; Q₁ is —N(R₇)— or —O—; E isC₁-C₃alkylene, the group —CH₂CH(R₈)—O— wherein R₈ is hydrogen, methyl orphenyl, the group —(CH₂)₃—NH— or a direct bond; R₇ is C₁-C₁₈alkyl,C₅-C₇-cycloalkyl, C₇-C₁₂aralkyl, cyanoethyl, C₆-C₁₀aryl, the group—CH₂CH(R₈)—OH; or a group of the formula

or a group of the formula

wherein G is C₂-C₆alkylene or C₆-C₁₂arylene and R is as defined above;or R₇ is a group —E—CO—NH—CH₂—OR₆; R₆ is hydrogen or C₁-C₁₈alkyl;Formula (F) denotes a recurring structural unit of a oligomer where T isethylene or 1,2-propylene, or is a repeating structural unit derivedfrom an α-olefin copolymer with an alkyl acrylate or methacrylate; k is2 to 100; R₁₀ is hydrogen, C₁-C₁₂alkyl or C₁-C₁₂alkoxy; T₂ has the samemeaning as R₄; T₃ and T₄ are independently alkylene of 2 to 12 carbonatoms, or T₄ is a group

T₅ is C₂-C₂₂alkylene, C₅-C₇cycloalkylene,C₁-C₄alkylenedi(C₅-C₇cycloalkylene), phenylene orphenylenedi(C₁-C₄alkylene); T₆ is

where a, b and c are independently 2 or 3, and d is 0 or 1; e is 3 or 4;T₇ and T₈ are independently hydrogen C₁-C₁₈alkyl, or T₇ and T₈ togetherare C₄-C₆alkylene or 3-oxapenthamethylene; E₁ and E₂, being different,each are —CO— or —N(E₅)—, where E₅ is hydrogen, C₁-C₁₂alkyl orC₄-C₂₂alkoxycarbonylalkyl; E₃ is hydrogen, alkyl of 1 to 30 carbonatoms, phenyl, naphthyl, said phenyl or said naphthyl substituted bychlorine or by alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12carbon atoms, or said phenylalkyl substituted by alkyl of 1 to 4 carbonatoms; E₄ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthylor phenylalkyl of 7 to 12 carbon atoms; or E₃ and E₄ together arepolymethylene of 4 to 17 carbon atoms, or said polymethylene substitutedby up to four alkyl groups of 1 to 4 carbon atoms; and E₆ is analiphatic or aromatic tetravalent radical.
 3. A compound according toclaim 1, wherein G₆ is hydrogen and G₅ is hydrogen or C₁-C₄alkyl.
 4. Acompound according to claim 1, wherein G₁, G₂, G₃ and G₄ areindependently C₁-C₄alkyl
 5. A compound according to claim 1, wherein G₁and G₃ are methyl and G₂ and G₄ are ethyl or propyl.
 6. A compoundaccording to claim 1, wherein G₁ and G₂ are methyl and G₃ and G₄ areethyl or propyl.
 7. A compound according to claim 1, wherein X isselected from the group consisting of —CH₂-aryl,

—CH₂—CH₂-aryl,

(C₅-C₆cycloalkyl)₂CCN, (C₁-C₁₂alkyl)₂CCN, —CH₂CH═CH₂,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₆-C₁₀)aryl,(C_(l)-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkoxy,(C₁-C₁₂)alkyl-CR₂₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₂₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl, wherein

R₂₀ is hydrogen or C₁-C₁₂alkyl; the aryl groups are unsubstituted orsubstituted with C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy,C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COOC₁-C₁₂alkyl.
 8. Acompound according to claim 1, wherein X is selected from the groupconsisting of —CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl,(C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂(C₁-C₈alkyl)CR₂₀—C(O)-phenyl, (C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈)alkoxy,(C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈)alkyl,(C₁-C₈)alkyl-CR₂₀—C(O)—N-di(C₁-C₈)alkyl,(C₁-C₈)alkyl-CR₂₀—C(O)—NH(C₁-C₈)alkyl, (C₁-C₈)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₈)alkyl.
 9. A compound according toclaim 1, wherein X is selected from the group consisting of —CH₂-phenyl,CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN,—CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl.
 10. A compound according toclaim 2 of formula A, B or O, wherein m is 1, R is hydrogen, C₁-C₁₈alkylwhich is uninterrupted or interrupted by one or more oxygen atoms,cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphaticcarboxylic acid having 2 to 18 carbon atoms, of a cycloaliphaticcarboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturatedcarboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylicacid having 7 to 15 carbon atoms; p is 1; R₁ is C₁-C₁₂alkyl,C₅-C₇cycloalkyl, C₇-C₈aralkyl, C₂-C₁₈alkanoyl, C₃-C₅alkenoyl or benzoyl;R₂ is C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₂-C₈alkenyl unsubstituted orsubstituted by a cyano, carbonyl or carbamide group, or is glycidyl, agroup of the formula —CH₂CH(OH)—Z or of the formula —CO—Z or —CONH—Zwherein Z is hydrogen, methyl or phenyl.
 11. A compound according toclaim 10, wherein R is hydrogen, C₁-C₁₈alkyl, cyanoethyl, benzoyl,glycidyl, a monovalent radical of an aliphatic, carboxylic acid; R₁ isC₁-C₁₂alkyl, C₇-C₈aralkyl, C₂-C₁₈alkanoyl, C₃-C₅alkenoyl or benzoyl; R₂is C₁-C₁₈alkyl, glycidyl, a group of the formula —CH₂CH(OH)—Z or of theformula —CO—Z, wherein Z is hydrogen, methyl or phenyl.
 12. A compoundaccording to claim 10 wherein G₆ is hydrogen and G₅ is hydrogen orC₁-C₄alkyl, G₁ and G₃ are methyl and G₂ and G₄ are ethyl or propyl or G₁and G₂ are methyl and G₃ and G₄ are ethyl or propyl.
 13. A compoundaccording to claim 10, wherein X is selected from the group consistingof —CH₂-phenyl, —CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN,(CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH₂, wherein R₂₀ is hydrogen or (C₁-C₄)alkyl. 14.A polymerizable composition, comprising a) at least one ethylenicallyunsaturated monomer or oligomer, and b) a 1-alkoxy-polyalkyl-piperidinederivative containing a structural element of formula (I)

G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl with the proviso that atleast one is not methyl or G₁ and G₂ or G₃ and G₄, or G₁ and G₂ and G₃and G₄ together form a C₅-C₁₂cycloalkyl group; G₅, G₆ independently areH, C₁-C₁₈alkyl, phenyl, naphthyl or a group COOC₁-C₁₈alkyl and Xrepresents a group having at least one carbon atom and is such that thefree radical X. derived from X is capable of initiating polymerizationof ethylenically unsaturated monomers, with the proviso that compoundsA1 and A2 are excluded


15. A composition according to claim 14, wherein the ethylenicallyunsaturated monomer or oligomer is selected from the group consisting ofethylene, propylene, n-butylene, i-butylene, styrene, substitutedstyrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone,vinylimidazole, maleic anhydride, (alkyl)acrylic acidanhydrides,(alkyl)acrylic acid salts, (alkyl)acrylic esters, (meth)acrylonitriles,(alkyl)acrylamides, vinyl halides or vinylidene halides.
 16. Acomposition according to claim 14 wherein the ethylenically unsaturatedmonomer is ethylene, propylene, n-butylene, i-butylene, isoprene,1,3-butadiene, α-C₅-C₁₈alkene, styrene, α-methyl styrene, p-methylstyrene or a compound of formula CH₂═C(R_(a))—(C═Z)—R_(b), wherein R_(a)is hydrogen or C₁-C₄alkyl, R_(b) is NH₂, O³¹ (Me⁺), glycidyl,unsubstituted C₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted by at least one Nand/or O atom, or hydroxy-substituted C₁-C₁₈alkoxy, unsubstitutedC₁-C₁₈alkylamino, di(C₁-C₁₈alkyl)amino, hydroxy-substitutedC₁-C₁₈alkylamino or hydroxy-substituted di(C₁-C₁₈alkyl)amino,—O—CH₂—CH₂—N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂An⁻; An⁻ is a anion of amonovalent organic or inorganic acid; Me is a monovalent metal atom orthe ammonium ion; Z is oxygen or sulfur.
 17. A composition according toclaim 16, wherein R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and Z isoxygen.
 18. A composition according to claim 14, wherein theethylenically unsaturated monomer is styrene, methylacrylate,ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate,hydroxyethylacrylate, hydroxypropylacrylate, dimethylaminoethylacrylate,glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate,butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide ordimethylaminopropyl-methacrylamide.
 19. A composition according to claim14, wherein the initiator compound is present in an amount of from 0.01mol-% to 30 mol-% , based on the monomer or monomer mixture.
 20. Aprocess for preparing an oligomer, a cooligomer, a polymer or acopolymer (block or random) by free radical polymerization of at leastone ethylenically unsaturated monomer or oligomer, which comprises(co)polymerizing the monomer or monomers/oligomers in the presence of aninitiator compound containing a structural element of formula (I)according to claim 1 under reaction conditions capable of effectingscission of the O—C bond to form two free radicals, the radical .X beingcapable of initiating polymerization.
 21. A process according to claim20, wherein the scission of the O—C bond is effected by ultrasonictreatment, heating or exposure to electromagnetic radiation, rangingfrom γ to microwaves.
 22. A process according to claim 20, wherein thescission of the O—C bond is effected by heating and takes place at atemperature of between 50° C. and 160° C.
 23. A1-oxy-polyalkyl-piperidine derivative containing a structural element offormula (II)

G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl with the proviso that atleast one is not methyl or G₁ and G₂ or G₃ and G₄, or G₁ and G₂ and G₃and G₄ together form a C₅-C₁₂cycloalkyl group; G₅, G₆ independently areH, C₁-C₁₈alkyl, phenyl, naphthyl or a group COOC₁-C₁₈alkyl, with theproviso that compounds B1, B2 and B3 are excluded


24. A polymerizable composition, comprising a) at least oneethylenically unsaturated monomer or oligomer, and b) a compound offormula (II) and c) a radical iniator X. capable of initiatingpolymerization of ethylenically unsaturated monomers.
 25. A process forpreparing an oligomer, a cooligomer, a polymer or a copolymer (block orrandom) by free radical polymerization of at least one ethylenicallyunsaturated monomer/oligomer, which comprises subjecting a compositionaccording to claim 24 to heat or actinic radiation.
 26. A polymer oroligomer, having attached at least one initiator group —X and at leastone oxyamine group of formula (Ia)

according to claim 23 wherein G₁, G₂, G₃, G₄, G₅ and G₆ are as definedin claim 1, obtainable by the process according to claim 20.